Non-aqueous electrolyte cell

ABSTRACT

The non-aqueous electrolyte battery of the present invention has a negative electrode comprising metallic lithium, a lithium alloy or a material capable of absorbing and desorbing lithium; a positive electrode; a non-aqueous electrolyte comprising a solvent and a solute dissolved in the solvent, wherein the above non-aqueous electrolyte contains at least one additive selected from phthalimide, derivative of phthalimide, phthalimidine, derivative of phthalimidine, tetrahydrophthalimide and derivative of tetrahydrophthalimide. On account of the effect of the above additive, the nonaqueous electrolyte battery of the present invention is not liable to cause an increase in the internal resistance during a long-term storage at high temperatures, and the charge/discharge cycle characteristics are improved in a secondary battery.

TECHNICAL FIELD

The present invention relates to a non-aqueous electrolyte battery. Morespecifically, the present invention relates to a non-aqueous electrolytecontaining an additive for suppressing an increase in the internalresistance of the battery.

BACKGROUND ART

In recent years, there has been a rapid advancement in the realizationof small and lightweight electronic devices, and along with that, therehas also been an increased demand for batteries having high energydensities. Accordingly, intensive researches have been made on lithiumprimary batteries having a negative electrode comprising metalliclithium as well as lithium ion secondary batteries having a negativeelectrode comprising a carbon material.

In such batteries, as a solvent for constituting the non-aqueouselectrolyte, propylene carbonate, ethylene carbonate, butylenecarbonate, sulfolane, γ-butyrolactone, dimethyl carbonate, diethylcarbonate, 1,2-dimethoxyethane, tetrahydrofuran, dioxolane and the likeare used singly or as a mixture. Further, as a solute to be dissolved inthe solvent, LiClO₄, LiPF₆, LiBF₄, LiCF₃SO₃, LiN(CF₃SO₂)₂, LiN(C₂F₅SO₂)₂are used singly or as a mixture.

Recently, intensive researches have been made on lithium polymerbatteries containing a gel non-aqueous electrolyte or a solid polymerelectrolyte. The gel nonaqueous electrolyte contains a host polymer forretaining the solute and the solvent as described above. The solidpolymer electrolyte is an electrolyte in which the polymer itselffunctions as the solvent for the solute, and a polymer similar to thehost polymer contained in the gel non-aqueous electrolyte is used, forexample.

As the polymers constituting these electrolytes, derivatives formed onthe basis of polyvinylidene fluoride, polyethylene oxide,polyacrylonitrile, polymethyl methacrylate, polysiloxane and the likeare used.

These constituting elements of the non-aqueous electrolytes are known tochemically react with moisture and the electrodes, and also with amaterial constituting a separator inside the battery. In particular,metallic lithium, lithium alloys such as LiAl, LiSn and the like andcarbon materials capable of absorbing and desorbing lithium, whichconstitute the negative electrode, are highly reactive with theconstituting elements of the non-aqueous electrolytes, and they form anorganic coating film on the surface of the negative electrode bychemical reactions and the like. In particular, such phenomena arelikely to occur when the batteries are stored in a high temperatureatmosphere of 80° C. or higher, or when the charge/discharge cycle isrepeated of the secondary batteries. Metal oxides often used as apositive electrode active material of the non-aqueous electrolytebatteries are known to dissolve in the non-aqueous electrolyte, and aphenomenon can be observed that materials dissolved are deposited on thesurface of the negative electrode to form a coating film.

Since these films have low electrical conductivity, they constitute acause for increasing the internal resistance of the batteries. Whenbatteries are stored for a long time, the voltage drop at dischargingdue to the increase of the internal resistance of the batteries isincreased, making it impossible to obtain satisfactory dischargecharacteristics. In secondary batteries, there is the problem that theinternal resistance of the batteries is increased by repetition of thecharge/discharge cycle, thereby deteriorating the cycle characteristics.

A-suggestion has been made intending to suppress the increase in theinternal resistance of the batteries by adding, to the non-aqueouselectrolyte, additives for forming a coating film on the surface of thenegative electrode. As such additives, aromatic dicarboxylic acid estersare mentioned in Japanese Laid-Open Patent Publication No. Hei 7-22069.These additives are effective for batteries stored at room temperature;however, they have no effects on batteries stored at high temperaturesor in which the charge/discharge cycle is repeated.

The present invention intends to prevent formation of an organic coatingfilm on the surface of the negative electrode caused by chemicalreactions when storing the nonaqueous electrolyte batteries at hightemperatures, to suppress an increase in the internal resistance inprimary batteries and secondary batteries, and to improve thecharge/discharge cycle characteristics of secondary batteries.

DISCLOSURE OF INVENTION

The present invention relates to a non-aqueous electrolyte batteryhaving a negative electrode comprising metallic lithium, a lithium alloyor a material capable of absorbing and desorbing lithium; a positiveelectrode; a solvent; and a solute dissolved in the solvent, wherein theabove non-aqueous electrolyte contains at least one additive selectedfrom the group consisting of compounds represented by the generalformula (1):

where X¹ to X⁴ are independently hydrogen atoms, F, Cl, Br, I or alkylgroups having 1 to 3 carbon atoms, Y¹ is a hydrogen atom, Na, K, Rb, Cs,Mg, Ca, Sr or Ba, and i is 1 or 2; compounds represented by the generalformula (2):

where X⁵ to X⁸ are independently hydrogen atoms, F, Cl, Br, I or alkylgroups having 1 to 3 carbon atoms, Y² is a hydrogen atom, Na, K, Rb, Cs,Mg, Ca, Sr or Ba, and j is 1 or 2; and compounds represented by thegeneral formula (3):

where Y³ is a hydrogen atom, Na, K, Rb, Cs, Mg, Ca, Sr or Ba, and k is 1or 2.

In the above non-aqueous electrolyte, the content of the above additiveis preferably 0.001 to 10% by weight relative to the sum of the solventand the solute.

The solute is preferably at least one selected from the group consistingof LiPF₆, LiBF₄, LiClO₄, LiCF₃SO₃, LiAsF₆, lithium salts represented bythe general formula (4):

LiN(C_(m)X⁹ _(2m+1)Z¹)₂,

lithium salts represented by the general formula (5):

LiC(C_(n)X¹⁰ _(2n+1)Z²)₃,

and lithium salts represented by the general formula (6):

LiCR(C_(p)X¹¹ _(2p+1)Z³)₂

where X⁹ to X¹¹ are independently F, Cl, Br or I; m, n and p areindependently integers of 1 to 4; and Z¹ to Z³ are independently CO orSO₂.

The aforementioned solvent preferably comprises at least one selectedfrom the group consisting of ethylene carbonate, propylene carbonate,butylene carbonate and γ-butyrolactone.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a longitudinal cross sectional view showing the structure ofthe non-aqueous electrolyte battery of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

The non-aqueous electrolyte contained in the nonaqueous electrolytebattery of the present invention includes a liquid non-aqueouselectrolyte and gel non-aqueous electrolyte. The liquid non-aqueouselectrolyte comprises an organic solvent as the solvent. The gelnon-aqueous electrolyte generally comprises the above liquid non-aqueouselectrolyte and a host polymer retaining thereof. The present inventionis characterized in an additive to be added to these non-aqueouselectrolytes.

In the non-aqueous electrolyte battery of the present invention, thenon-aqueous electrolyte contains at least one additive selected from thegroup consisting of compounds represented by the general formula (1):

where X¹ to X⁴ are independently hydrogen atoms, F, Cl, Br, I or alkylgroups having 1 to 3 carbon atoms, Y¹ is a hydrogen atom, Na, K, Rb, Cs,Mg, Ca, Sr or Ba, and i is 1 or 2 (phthalimide or a derivative ofphthalimide); compounds represented by the general formula (2):

where X⁵ to X⁸ are independently hydrogen atoms, F, Cl, Br, I or alkylgroups having 1 to 3 carbon atoms, Y² is a hydrogen atom, Na, K, Rb, Cs,Mg, Ca, Sr or Ba, and j is 1 or 2 (phthalimidine or a derivative ofphthalimidine); and compounds represented by the general formula (3):

where Y³ is a hydrogen atom, Na, K, Rb, Cs, Mg, Ca, Sr or Ba, and k is 1or 2 (tetrahydrophthalimide or a derivative of tetrahydrophthalimide).

In the case where at least one selected from X¹ to X⁸ is other than ahydrogen atom and the remainders are hydrogen atoms, the one other thana hydrogen atom is preferably an alkyl group or a fluorine atom.

Here, in the case where one of X¹ to X⁴ is an alkyl group and theremainders are hydrogen atoms, X² or X³ is preferably an alkyl group. Onthe other hand, one of X⁵ to X⁸ is an alkyl group and the remainders arehydrogen atoms, X⁶ or X⁷ is preferably an alkyl group and morepreferably X⁶ is an alkyl group. In any of the above, an ethyl group isparticularly preferable as the alkyl group.

In the case where two of X¹ to X⁴ are fluorine atoms and the remaindersare hydrogen atoms, X² and X³ are preferably fluorine atoms. Also, twoof X⁵ to X⁸ are fluorine atoms and the remainders are hydrogen atoms, itis preferable that X⁶ and X⁷ are fluorine atoms.

In the formulae (1) to (3), in the case where Y¹ to Y³ are divalentatoms, for example, Mg, Ca, Sr or Ba, and the above additive has twoorganic anions, the two organic anions may be the same or different.

The compounds represented by the general formulae (1) to (3) areconsidered to react with the negative electrode in preference to theorganic solvent which is a constituting element of the non-aqueouselectrolyte and form stable coating films having a similar structure tothat of phthalimide, phthalli dine or the like to suppress reaction ofthe organic solvent with the negative electrode. In addition, the formedcoating films are considered to have a good lithium ion conductivity andhardly increase the internal resistance of the batteries as conventionaladditives do.

The compounds represented by the general formulae (1) to (3) includephthalimide, 2-ethylphthalimide, 2-fluorophthalimide, potassiumphthalimide, potassium 2-ethylphthalimide, potassium2-fluorophthalimide, phthalimidine, 2-ethylphthalimidine,2-fluorophthalimidine, potassium phthalimidine, potassium2-ethylphthalimidine, potassium 2-fluorophthalimidine,tetrahydrophthalimide, sodium tetrahydrophthalitmide, potassiumtetrahydrophthalimide, magnesium tetrahydrophthalimide, calciumtetrahydrophthalimide, strontium tetrahydrophthalimide and the like.

Among these, phthalimide, 2-ethylphthalimide, 2-fluorophthalimide,phthalimidine, 2-ethylphthalimidine, 2-fluorophthalimidine,tetrahydrophthalimide and potassium tetrahydrophthalimide are the mostpreferable in view of the stability of the coating film formed on thesurface of the negative electrode, and also because they have a lowreactivity with the positive electrode, the negative electrode, and thesolvent and the solute in the. non-aqueous electrolyte.

In the non-aqueous electrolyte, the amount of the additive is preferably0.001 to 10% by weight, and more preferably 0.001 to 1% by weightrelative to the sum of the solvent and the solute.

As the solute, for example LiClO₄, LiPF₆, LiBF₄, LiCF₃SO₃, LiN(CF₃SO₂)₂,LiN(C₂F₅SO₂)₂, LiN(CF₃SO₂)(C₄F₉SO₂) and the like can be used. They maybe used singly or as a mixture of two or more of them. The concentrationof the solute in the non-aqueous electrolyte is preferably in the rangeof 0.2 to 2.0 mol/liter.

As the organic solvents constituting the liquid nonaqueous electrolyte,it is preferable to mix an organic solvent having a high remittivitysuch as ethylene carbonate, propylene carbonate, butylene carbonate,γ-butyrolactone, sulfolane and vinylene carbonate with an organicsolvent having a low viscosity such as dimethyl carbonate, ethyl methylcarbonate, diethyl carbonate and 1,2-dimethoxyethane. In particular, anorganic solvent containing at least one selected from the groupconsisting of ethylene carbonate, propylene carbonate, butylenecarbonate and γ-butyrolactone are preferred.

As the host polymer in the gel non-aqueous electrolyte, a derivative onthe basis of polyvinylidene fluoride, polyethylene oxide,polyacrylonitrile, polymethyl methacrylate, polysiloxane and the likecan be mentioned.

By combining the aforementioned non-aqueous electrolyte with the givenpositive electrode and negative electrode, primary batteries which arenot liable to cause an increase in the internal resistance during along-term storage of the batteries, as well as secondary batterieshaving excellent charge/discharge cycle characteristics at hightemperatures can be obtained.

The positive electrode can be prepared by using materials which havebeen conventionally used in the positive electrode of non-aqueouselectrolyte batteries. Usable materials for the positive electrode are,for example, metal oxides such as LiCoO₂, LiNiO₂, LiMn₂O₄, LiMnO₂, V₂O₅,V₆O₁₃, MnO₂, WO₃, Nb₂O₅ and Li_(4/3)Ti_(5/3)O₄, carbon fluoriderepresented by CF_(x)(x≦1), sulfides such as FeS₂ and TiS₂, andconductive polymers such as polypyrrole and polyaniline.

The negative electrode can also be prepared by using materials whichhave conventionally been used in the negative electrode of non-aqueouselectrolyte batteries. Usable materials for the negative electrode aremetallic lithium, lithium alloys such as LiAl, LiSi, LiSn, LiNiSi, andLiPb, carbon materials such as graphite and coke which can absorb anddesorb lithium, metal oxides such as SiO, SnO, Fe₂O₃, WO₂, Nb2O₅ andLi_(4/3)Ti_(5/3)O₄, and nitride such as Li_(0.4)CoN.

Next, the present invention will be described with reference toexamples.

EXAMPLE 1

FIG. 1 shows a longitudinal sectional view of a coin type battery usedin this example. The numeral 2 and 6 are respectively a positiveelectrode case and a negative electrode case each made of stainlesssteel, and the numeral 5 is an insulating packing made of polypropylene.The numeral 1 is a positive electrode and 4 is a negative electrode. Thenumeral 3 is a separator comprising a non-woven fabric made ofpolypropylene. This battery is 20 mm in outer diameter and 2.5 mm inheight.

A positive electrode material mixture was obtained by mixing LiCoO₂powder as a positive electrode active material, a carbon powder as aconductive agent and a fluorocarbon polymer as a binder in a weightratio of 80:10:10 followed by drying the mixture. This positiveelectrode material mixture was molded by pressing at 2 ton/cm² into apellet of 16 mm in diameter and 0.9 mm in thickness, and then dried at250° C. in a dried atmosphere containing 1% or less of moisture, therebygiving a positive electrode.

On the other hand, a negative electrode material mixture was obtained bymixing a natural graphite powder as a negative electrode active materialand a fluorocarbon polymer as a binder in a weight ratio of 85:15. Thisnegative electrode material mixture was molded by pressing at 2 ton/cm²into a pellet of 16 mm in diameter and 0.9 mm in thickness, and thendied at 110° C. in a dried atmosphere containing 1% or less of moisture,thereby to give a negative electrode.

Ethylene carbonate and diethyl carbonate were mixed in a volume ratio of5:5 to give a solvent of the non-aqueous electrolyte. In this solvent,LiPF₆ was dissolved as a solute in a rate of 1.0 mol/liter. In thenon-aqueous electrolyte obtained, an additive A1, B1, C1 or D1 as shownin Table 1; A2, D2, C2 or D2 as shown in Table 2; and A3 or B3 as shownin Table 3 were added in a rate of 0.1% by weight relative to the totalweight of the solvent and LiPF₆.

TABLE 1 Additive Constitution A1

B1

C1

D1

TABLE 2 Additive Constitution A2

B2

C2

D2

TABLE 3 Additive Constitution A3

B3

Using the non-aqueous electrolytes containing the obtained additives,the positive electrode and the negative electrode, coin type batteriesA1, B1, C1, D1, A2, B2, C2, D2 A3 and B3 as described above wereprepared. The amounts of the non-aqueous electrolytes to be poured inthe batteries were 100 mg.

Also, as a comparative example, using a non-aqueous electrolytecontaining no additive, similar battery 1 was prepared.

Next, with each battery, the following evaluation was made.

The batteries were charged at a constant current of 1 mA/cm² until 4.2V, and the internal resistance of the batteries was measured.Subsequently, in the charged state, batteries A1 to D1, A2 to D2 andbattery 1 were stored in a constant-temperature bath at 60° C. for twomonths, and batteries A3 and B3 were stored in a constant-temperaturebath at 85° C. for 20 days. Then, the internal resistance of thebatteries after the storage was measured. The internal resistance wasmeasured at an alternating current of 1 kHz. The results are shown inTable 4.

TABLE 4 Internal resistance of the battery (Ω) After Before Aftercharge/discharge Battery Additive storage storage cycle Battery A1 A112.3 14.1 14.4 Battery B1 B1 13.0 14.4 14.6 Battery C1 C1 12.2 12.5 12.7Battery D1 D1 12.1 12.3 12.4 Battery A2 A2 12.8 14 2 14.5 Battery B2 B213.5 14.5 14.7 Battery C2 C2 12.7 12.9 13.3 Battery D2 D2 12.6 12.7 13.1Battery A3 A3 12.5 14.2 14.8 Battery B3 B3 13.3 14.6 15.0 Battery 1 none11.3 20.4 21.2

On the other hand, the charge/discharge cycle is repeated for 100 timesat a constant current of 1 mA/cm² in a voltage range of 3.0 to 4.2 V;subsequently, the internal resistance of the batteries was measured. Theresults are shown in Table 4.

In Table 4, all the batteries to which additives were added have astable internal resistance compared to battery 1 containing no additive,and show smaller increase in the internal resistance caused by thestorage at high temperatures and repetition of the charge/dischargecycle.

The batteries, to which an additive D1 or D2 among the above additiveswas added, show the best results.

EXAMPLE 2

In this example, button type batteries having the structure as shown inFIG. 1 were prepared in the following manner.

Electrolytic manganese dioxide which had been thermally treated at 400°C. , a carbon powder as a conductive agent and a fluorocarbon polymer asa binder were mixed in a weight ratio of 80:10:10 to give a positiveelectrode material mixture. This positive electrode material mixture wasmolded by pressing at 2 ton/cm² into a pellet of 16 mm in diameter anddried at 250° C. in a dried atmosphere containing 1% or less ofmoisture, thereby to give a positive electrode.

In the negative electrode, metallic lithium was used. Specifically, arolled lithium plate was punched into a given size and fixed on theinner side of the negative electrode case 6.

Propylene carbonate and 1,2-dimethoxyethane were mixed in a volume ratioof 5:5 to give a solvent of the non-aqueous electrolyte. In thissolvent, LiCF₃SO₃ as a solute was dissolved in a rate of 1 mol/liter. Tothe non-aqueous electrolyte obtained, an additive A1, B1, C1 or D1 asshown in Table 1; an additive A2, D2, C2 or D2 as shown in Table 2; andan additive A3 or B3 as shown in Table 3 was added in a rate of 0.1% byweight relative the total weight of the above solvent and LiCF₃SO₃.

Using the obtained non-aqueous electrolytes, the positive electrode andthe negative electrode, coin type batteries A1′, B1′, C1′, D1′, A2′,B2′, C2′, D2′, A3′ and B3′ as described above were prepared. The amountof the non-aqueous electrolyte to be poured into the batteries was 160mg.

Also, as a comparative example, a similar battery 2 was prepared using anon-aqueous electrolyte containing no additive.

Next, with each battery, the following evaluation was made.

After the internal resistance of the batteries was measured, batteriesA1′ to D1′, A2′ to D2′ and battery 2 were stored in aconstant-temperature bath at 60° C. for two months, and batteries A3′and B3′ were stored in a constant-temperature bath at 85° C. for 20days. Then, the internal resistance after the storage of the batterieswas measured. The internal resistance was measured at an alternatingcurrent of 1 kHz. The results are shown in Table 5.

TABLE 5 Internal resistance of the battery (Ω) Battery Additive Beforestorage After storage Battery A1′ A1 10.1 11.4 Battery B1′ B1 9.1 10.1Battery C1′ C1 8.6 9.2 Battery D1′ D1 8.4 8.9 Battery A2′ A2 10.6 11.3Battery B2′ B2 9.8 10.1 Battery C2′ C2 9.2 9.5 Battery D2′ D2 8.9 9.1Battery A3′ A3 10.5 13.3 Battery B3′ B3 9.8 12.8 Battery 2 none 8.2 15.3

In table 5, all the batteries to which additives were added have astable internal resistance compared to battery 2 containing no additiveand have smaller increase in the internal resistance caused by thestorage at high temperatures.

EXAMPLE 3

A battery similar to battery D1′ in Example 2 was prepared except thatthe addition rate of additive D1 was 0.0005 to 15% by weight relative tothe total weight of the solvent and LiCF₃SO₃. Then, evaluation similarto battery D1's in Example 2 was made. The results are shown in Table 6.

TABLE 6 Added amount of D1 Internal resistance of the battery (Ω) (wt %)Before storage After storage 0 8.2 15.3 0.0005 8.2 13.9 0.001 8.3 9.20.01 8.3 9.0 0.1 8.4 8.9 1.0 8.6 9.3 10 8.8 9.7 15 13.1 14.6

A battery similar to battery D2′ in Example 2 was prepared except thatthe addition rate of additive D2 was 0.0005 to 15% by weight relative tothe total weight of the LiCF₃SO₃. Then, evaluation similar to batteryD2's In Example 2 was made. The results are shown in Table 7.

TABLE 7 Added amount of D2 Internal resistance of the battery (Ω) (wt %)Before storage After storage 0 8.2 15.3 0.0005 8.3 13.2 0.001 8.5 9.30.01 8.6 8.9 0.1 8.9 9.1 1.0 9.1 9.3 10 9.5 9.9 15 13.6 14.9

A battery similar to battery A3′ in Example 2 was prepared except thatthe addition rate of additive A3 was 0.0005 to 15% by weight relative tothe total weight of the solvent and LiCF₃SO₃. Then, evaluation similarto battery A3's in Example 2 was made. The results are shown, in Table8.

TABLE 8 Added amount of A3 Internal resistance of the battery (Ω) (wt %)Before storage After storage 0 8.2 21.5 0.0005 8.5 19.8 0.001 8.9 15.20.01 9.6 13.8 0.1 10.5 13.3 1.0 10.8 13.3 10 12.5 14.5 15 13.8 17.2

In Tables 6 to 8, when the addition rate of the additives relative tothe sum of the solvent and LiCF₃SO₃ is in the range of 0.001 to 10.0% byweight, an increase in the internal resistance is particularly reduced.

In the case where the addition rate of the additives relative to the sumof the solvent and LiCF₃SO₃ was less than 0.001% by weight, the effectfor suppressing an increase in the internal resistance is not displayedso much. On the other hand, in the case where the addition rate was10.0% by weight or more, an increase in the internal resistance due tothe additive itself is observed. Also, when the addition rate is in therange of 0.01 to 1.0% by weight, best results can be obtained. In thecase where similar evaluation was made using additives other than D1, D2and A3, similar tendency was observed.

In Example 3, the effects of the present invention were explained in thecase of primary batteries; however, in the case of secondary batteries,in addition to the effect for suppressing an increase in the internalresistance during storage at high temperatures, an effect for improvingthe charge/discharge cycle characteristics was also observed.

In each of the above examples, coin type batteries were prepared;however, the present invention is also applicable to batteries of othershapes such as cylindrical and square type batteries.

In the above examples, explanation was made about the liquid non-aqueouselectrolyte; however, the present invention is also applicable tobatteries using the gel non-aqueous electrolyte and the solid polymerelectrolyte.

INDUSTRIAL APPLICABILITY

According to the present invention, non-aqueous electrolyte batterieswhich are not liable to cause an increase in the internal resistanceduring a long-term storage at high temperatures, and in secondarybatteries, in addition to that, the charge/discharge cyclecharacteristics are improved.

What is claimed is:
 1. A non-aqueous electrolyte battery having anegative electrode comprising metallic lithium, a lithium alloy or amaterial capable of absorbing and desorbing lithium; a positiveelectrode; and a non-aqueous electrolyte comprising a solvent and asolute dissolved in said solvent, wherein said non-aqueous electrolytecontains at least one additive selected from the group consisting ofcompounds represented by the general formula (1):

where X¹ to X⁴ are independently hydrogen atoms, F, Cl, Br, I or alkylgroups having 1 to 3 carbon atoms, Y¹ is a hydrogen atom, Na, K, Rb, Cs,Mg, Ca, Sr or Ba, and i is 1 or 2; compounds represented by the generalformula (2):

where X⁵ to X⁸ are independently hydrogen atoms, F, Cl, Br, I or alkylgroups having 1 to 3 carbon atoms, Y² is a hydrogen atom, Na, K, Rb, Cs,Mg, Ca, Sr or Ba, and j is 1 or 2; and compounds represented by thegeneral formula (3):

where Y³ is a hydrogen atom, Na, K, Rb, Cs, Mg, Ca, Sr or Ba, and k is 1or
 2. 2. The non-aqueous electrolyte battery in accordance with claim 1,wherein the content of said additive in said non-aqueous electrolyte is0.001 to 10% by weight relative to the sum of said solvent and saidsolute.
 3. The non-aqueous electrolyte battery in accordance with claim1, wherein said solute is at least one selected from the groupconsisting of LiPF₆, LiBF₄, LiClO₄, LiCF₃SO₃, LiAsF₆, lithium saltsrepresented by the general formula (4): LiN(C_(m)X⁹ _(2m+1)Z¹)₂, lithiumsalts represented by the general formula (5): and LiC(C_(n)X¹⁰_(2n+1)Z²)₃, lithium salts represented by the general formula (6):LiCR(C_(p)X¹¹ _(2p+1)Z³)₂ where X⁹ to X¹¹ are independently F, Cl, Br orI; m, n and p are independently integers of 1 to 4; and Z¹ to Z³ areindependently CO or SO₂.
 4. The non-aqueous electrolyte battery inaccordance with claim 1, wherein said solvent comprises at least oneselected from the group consisting of ethylene carbonate, propylenecarbonate, butylene carbonate and γ-butyrolactone.